Computational and Theoretical Chemistry最新文献

Catalytic pyrolysis mechanism of tetrabromobisphenol A by calcium oxide: A density functional theory study 氧化钙催化四溴双酚 A 的热解机理：密度泛函理论研究

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2024-11-12 DOI: 10.1016/j.comptc.2024.114987

Jiankai Ou , Lufang Zhao , Yang Long , Yu Jiang , Xin Mu , Jinbao Huang , Hong Wang

{"title":"Catalytic pyrolysis mechanism of tetrabromobisphenol A by calcium oxide: A density functional theory study","authors":"Jiankai Ou , Lufang Zhao , Yang Long , Yu Jiang , Xin Mu , Jinbao Huang , Hong Wang","doi":"10.1016/j.comptc.2024.114987","DOIUrl":"10.1016/j.comptc.2024.114987","url":null,"abstract":"<div><div>In this paper, the mechanisms of catalytic pyrolysis of tetrabromobisphenol A (TBBPA) by calcium oxide (CaO) were studied through density functional theory methods. The results indicate that the phenolic hydroxyl group of TBBPA is the preferred site for CaO to extract protons, and the generated anion further transforms into 2,6-dibromophenol via demethylation and hydrogen transfer reactions. The reaction activity of CaO with hydrogen bromide is relatively high, with an energy barrier of 133.2 kJ/mol. CaO produces calcium ions, which combine with bromine ions to form calcium bromide to achieve the purpose of fixing bromine. In addition, the participation of calcium ions results in the O<img>H bond being easier to crack, which further lowers the reaction energy barrier of keto-enol tautomerism reactions H2O produced during catalytic pyrolysis also has an obvious catalytic effect, and the energy barrier of the keto-enol tautomerism reaction decreased from 309.1 kJ/mol to 150.6 kJ/mol with the participation of H2O.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114987"},"PeriodicalIF":3.0,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657024","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Cation–anion chalcogen bonds in ion pairs: A combined crystallographic survey and computational investigation 离子对中的阳离子-阴离子缩醛键：晶体学调查与计算研究的结合

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2024-11-12 DOI: 10.1016/j.comptc.2024.114985

Hui Liu , Zijian Han , Yunxiang Lu , Zhijian Xu , Weiliang Zhu

引用次数: 0

Research on N, Ne, and P adsorption on boron-germanene nanoribbons for nano sensor applications 用于纳米传感器应用的硼-锗纳米带对 N、Ne 和 P 的吸附研究

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2024-11-12 DOI: 10.1016/j.comptc.2024.114988

Hoang Van Ngoc, Huynh Thi Phuong Thuy

{"title":"Research on N, Ne, and P adsorption on boron-germanene nanoribbons for nano sensor applications","authors":"Hoang Van Ngoc, Huynh Thi Phuong Thuy","doi":"10.1016/j.comptc.2024.114988","DOIUrl":"10.1016/j.comptc.2024.114988","url":null,"abstract":"<div><div>The study investigated the adsorption of N, P, and Ne atoms on boron-germanene nanoribbons (BGeNRs) using density functional theory (DFT) and the Vienna Ab initio Simulation Package (VASP). Results indicated that both the pristine and adsorbed configurations exhibited metallic behavior. While the pristine and Ne-adsorbed configurations were nonmagnetic, the N- and P-adsorbed configurations displayed magnetic moments of 1.81 μB and 1.21 μB, respectively. The N-adsorbed configuration had the lowest adsorption energy, whereas the Ne-adsorbed configuration exhibited a positive adsorption energy. Multi-orbital hybridization analysis revealed that hybridization processes predominantly occurred in the conduction band at energy levels corresponding to the σ bond. Charge density difference analysis showed significant charge transfer between the substrate and the adsorbed elements. Additionally, optical properties, including the real and imaginary parts of the dielectric function, absorption coefficient, and electron-hole density, were systematically examined to highlight the variations. The findings underscore the potential application of BGeNR materials in nanosensors.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114988"},"PeriodicalIF":3.0,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657518","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Geometrical features and chemical adsorptions of (Ag3Sn)n clusters (Ag3Sn)n 簇的几何特征和化学吸附作用

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2024-11-12 DOI: 10.1016/j.comptc.2024.114986

Qiman Liu , Manli Zhang

{"title":"Geometrical features and chemical adsorptions of (Ag3Sn)n clusters","authors":"Qiman Liu , Manli Zhang","doi":"10.1016/j.comptc.2024.114986","DOIUrl":"10.1016/j.comptc.2024.114986","url":null,"abstract":"<div><div>The Ag-Sn alloys are famous ancient intermetallics, with the Ag3Sn being a crucial component of the phase diagram. Recently, Ag3Sn nanoparticles showcase efficient catalytic CO oxidation capabilities. Here, structural features and stability of (Ag3Sn)n (n = 1–6) clusters are first analyzed in detail. The results reveal that structures of them evolve from cages to close-packed icosahedra, where Ag are distributed on cores and gradually aggregated, whereas Sn occupy edge positions and become dispersed. Moreover, the icosahedral (Ag3Sn)3 has a higher stability than that of its neighbors and can maintain the structural integrity at 700 K. The molecular orbitals reveal that the (Ag3Sn)3 has an electronic open-shell configuration of 1S21P61D102S21F1, which is confirmed by the density of states. Electrostatic potential surfaces show that (Ag3Sn)n have significant electron-deficient σ-hole regions at Ag sites, which can make C<img>O stretching frequencies and bond lengths have red-shifts. Adsorption energies between (Ag3Sn)n and CO display odd–even oscillations, ranging from (0.43–0.68) eV, and the direction of charge flows is from CO → clusters. Our work provides inferences to structure evolutions and adsorptions of the Ag3Sn alloy at the atomic level.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114986"},"PeriodicalIF":3.0,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657676","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Influence of 2,1,3-pyrazinochalcogenadiazoles structure on their dimerization via chalcogen bonding (chalcogen = S, Se, Te) 2,1,3-吡嗪基胆原二唑结构对其通过胆原键（胆原 = S、Se、Te）进行二聚化的影响

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2024-11-09 DOI: 10.1016/j.comptc.2024.114984

Qiaoyu Wei , Hui Wang , Andrey V. Zibarev

{"title":"Influence of 2,1,3-pyrazinochalcogenadiazoles structure on their dimerization via chalcogen bonding (chalcogen = S, Se, Te)","authors":"Qiaoyu Wei , Hui Wang , Andrey V. Zibarev","doi":"10.1016/j.comptc.2024.114984","DOIUrl":"10.1016/j.comptc.2024.114984","url":null,"abstract":"<div><div>Chalcogen bonding (ChB) is an σ-hole-driven secondary bonding interaction (SBI). The crystalline 2,1,3-benzochalcogenadiazoles involved in organic optoelectronics is exemplified by [E···N]2 supramolecular synthon. For 5,6- R2 −2,1,3-pyrazinochalcogenadiazoles E-M and [E···N]2-bonded (E-M)2 (E = S, Se, Te; R/M = H/1, Me/2, CN/3), gas-phase and dichloromethane solution calculations are performed. The molecular electrostatic potential suggests that changes in E, R influence σ- and π-holes of E-M/(E-M)2. Distant R acts via long-range electrostatic field effect. ChB strength increases in the order S < Se < Te, and (E-2)2 < (E-1)2 < (E-3)2. The main driving forces are electrostatic and dispersion interactions. Crystalline S-1 and Se-2 have head-to-head dimers. Se-3 shows head-to-tail chains via Se···Ncyano ChB. A competition between different ChB, and, between ChB and other SBIs, should be considered in the design and synthesis of new E-M/(E-M)2 for fundamentals and applications.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114984"},"PeriodicalIF":3.0,"publicationDate":"2024-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657677","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

The limits of copper oxidation states from density functional theory computations: Fluoro-copper complexes, [CuFn]x, where n = 1 through 6 and x = 3+ through 5− 密度泛函理论计算得出的铜氧化态极限：氟铜络合物 [CuFn]x，其中 n = 1 至 6，x = 3+ 至 5-

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2024-11-09 DOI: 10.1016/j.comptc.2024.114942

Hanna D. Hobbs, Lowen M. Hobbs, Robert W. Zoellner

{"title":"The limits of copper oxidation states from density functional theory computations: Fluoro-copper complexes, [CuFn]x, where n = 1 through 6 and x = 3+ through 5−","authors":"Hanna D. Hobbs, Lowen M. Hobbs, Robert W. Zoellner","doi":"10.1016/j.comptc.2024.114942","DOIUrl":"10.1016/j.comptc.2024.114942","url":null,"abstract":"<div><div>Density functional theory calculations, at the ωB97X-D/6-311+G* level of theory, were performed on homoleptic fluoro-copper complexes [CuFn]x, n = 1 through 6 and x = 3+ through 5−, to determine the highest positive and lowest negative copper oxidation states that can be supported in these complexes. Only singlet and doublet spin states were investigated. All fluoro-copper stoichiometries stabilized copper(III) or greater. However, some stoichiometries stabilized oxidation states up to copper(VI), and the greatest positive copper oxidation state was copper(VIII) in the distorted octahedral [CuF6]2+ cation. Oxidation states as negative as copper(–IV) in the diatomic [CuF]5− anion and copper(–III) in the triatomic [CuF2]5− were also observed as optimized minima, although no negative oxidation states were calculated to exist for fluoro-copper complexes containing more than two fluorine atoms. No singlet or doublet fluoro-copper complexes with charges more positive than 3+, more negative than 5−, or of Cu(VII), could be optimized.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114942"},"PeriodicalIF":3.0,"publicationDate":"2024-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657038","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Computational screening and investigation of ligand effect on TM single atom catalyst for hydrogen evolution reaction 计算筛选和研究配体对 TM 单原子氢进化反应催化剂的影响

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2024-11-08 DOI: 10.1016/j.comptc.2024.114981

N.J. Hemavathi , Chiranjib Majumder , Suman Kalyan Sahoo

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The non-covalent interaction between C3N and H2 C3N 和 H2 之间的非共价相互作用

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2024-11-08 DOI: 10.1016/j.comptc.2024.114951

Yue-hong Yin, Chao Lu

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Molecular design of furanoacene-based singlet fission sensitizers combining diradical character and cross-substitution 基于呋喃并烯的单子裂变敏化剂的分子设计，兼具二拉基特性和交叉取代性

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2024-11-08 DOI: 10.1016/j.comptc.2024.114982

Li shen, Zhanqing Chang, Changhao Zhang, Mengyao Zhu, Xiaobo Gao, Xinwei Liu, Yue Li, Jitao Lu, Qian Wu, Qingguo Meng

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Designing and investigating electronic states of porphyrin Schiff bases nanoflakes, cathode materials for K+ - batteries 设计和研究卟啉席夫碱纳米片的电子状态，K+ - 电池的阴极材料

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2024-11-07 DOI: 10.1016/j.comptc.2024.114936

Fazal Dayan, Adnan Shahzad, Imad Ud Din

{"title":"Designing and investigating electronic states of porphyrin Schiff bases nanoflakes, cathode materials for K+ - batteries","authors":"Fazal Dayan, Adnan Shahzad, Imad Ud Din","doi":"10.1016/j.comptc.2024.114936","DOIUrl":"10.1016/j.comptc.2024.114936","url":null,"abstract":"<div><div>Identifying new electrode materials for K-ion batteries (KIBs) is still difficult since battery technology lacks an effective high-throughput screening approach. The durability, affordability, safety, and resemblance to Li-ion batteries of KIBs have garnered them tremendous attention. Porphyrin-based materials have become attractive options because of their generous surface area and advantageous photo-physical characteristics. As effective cathodic materials for KIBs, porphyrin Schiff base nanostructures (SBNs) are suggested in this work. Our goal was to improve Potassium-ion doped porphyrin derivatives by using Density Functional Theory (DFT) with the Gaussian 09 program with a B3LYP/6-31G(d) basis set. We also calculated important electronic parameters such as the band gap, electrophilicity, chemical potential, and frontier orbitals (HOMO and LUMO). The determined HOMO-LUMO gaps for compounds 1 to 4 were 2.97, 1.52, 1.38, and 1.36 respectively. The computed gaps indicate that the reactivity of the compounds increases from 1 to 4, whereas the stability decreases from 1 to 4.</div><div>Based on these computational observations, it is expected that this theoretical analysis will provide a basis for future researchers to explore the practical applications of these compounds through experimentation.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114936"},"PeriodicalIF":3.0,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657675","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0